The present invention relates to an automatic processing machine for silver halide photographic light-sensitive materials, more specifically a compact automatic processing machine offering markedly improved operability free of dissolving operation and remarkably improved chemical stability.
Silver halide color photographic light-sensitive materials (hereinafter also referred to as light-sensitive materials or photographic materials) are processed in developing, desilvering, washing, stabilizing and other processes after exposure. Silver halide black-and-white photographic light-sensitive materials are developed and fixed after exposure. A black-and-white developer or a color developer, a bleacher or a bleach-fixer, a fixer, tap water or deionized water, a stabilizing solution and a dye stabilizer are used for development, desilvering, fixing, washing, waterless washing and dye stabilization, respectively.
The liquids capable of performing these processes are called processing solutions. Each processing solution is usually kept at a temperature of 30.degree. to 40.degree. C., in which the light-sensitive material is immersed and processed.
These processes are usually carried out by sequentially transporting the light-sensitive material through processing tanks containing the above processing solutions, using an automatic processing machine or another means.
The automatic processing machine mentioned herein is generally a processing machine having a developing portion, a fixing portion, a desilvering portion, a washing or stabilizing portion and a drying portion, and a means for automatically sequentially transporting the photographic light-sensitive material to the processing tanks.
In carrying out processing using such an automatic processing machine, the processing solution in each processing tank is supplemented with a processing agent to keep the activity of the processing solution in the processing tank constant.
For this purpose, it is common to prepare a replenisher containing the processing agent dissolved therein.
Specifically, processing is carried out while supplying the previously prepared replenisher from the replenisher tank to the processing tank as appropriate.
In this case, it is the common practice to prepare the replenisher itself to be stored in the replenisher tank in a remove place, and in mini-labs etc., the replenisher is usually prepared in a given amount in a replenisher tank made within the processing machine at a time by manual dissolution or mixing dissolution using a mechanical mixer.
The silver halide photographic light-sensitive material processing agent (hereinafter also referred to as photographic processing agent) is supplied in the form of powder or liquid; it is prepared as a solution in a given amount of water in the case of powder. In the case of liquid, it is prepared as a dilution in a given amount of water in the case of liquid, since it is supplied in a concentrated state.
Replenisher tanks may be set by the automatic processing machine, requiring considerable space. Also, in recently-increasing mini-labs, replenisher tanks are housed in the automatic processing machine; in this case as well, sufficient space must be available for the replenisher tanks, each of which should contain at least 5 to 10 liter of replenisher.
Any processing agent for replenishment is divided in some parts to ensure constantly good performance in photographic processing. For example, the color developer replenisher is divided in three or four parts, and the bleach-fixer replenisher for color photography is divided in two parts: a part of the oxidant ferric salt of organic acid and a part of the reducing agent thiosulfate. In preparing the replenisher, said dense part of ferric salt of organic acid and said dense part of thiosulfate are mixed together and diluted with a given amount of water before using.
Said dense parts are placed in containers such as plastic containers, which containers are packed in outer packages, such as corrugated cardboard boxes, for 1 unit of commercial distribution.
The processing agent for replenishment in a kit of part agents is dissolved, diluted, mixed and then diluted to a given volume before using. Said processing agent for replenishment has the following drawbacks:
First, almost all conventional kits comprise dense aqueous solutions concentrated for improved operability, most of which are very dangerous because of high pH values of not more than 2.0 or not less than 12.0 in that they are harmful to the human body by skin contact etc. Also, many of them are strong oxidants or reducing agents, possessing very dangerous corrosivity in transport by ships or aircraft. The aqueous solution is subject to limitation as to solubility, being heavier and bulkier than in the case of solid. Since the concentrated solution is a dangerous article as stated above, its containers must be sufficiently tough to avoid destruction and spillage even if it is fallen; plastic container disposal poses a problem.
Second, the part agents are removely contained in respective containers; some processing agents for replenishment comprise several bottles of part agents so that each unit of commercial distribution thereof involves a considerable number of containers, which requires much space for storage and transportation. For example, the color developer replenishing agent for CPK-2-20QA, a processing solution for color printing paper, is available in 10-liter units, wherein part A (a kit including a preservative), part B (a kit including a color developing agent) and part C (alkaline agent) are each contained in a 500-ml plastic container. Similarly, the bleach-fixer replenisher is available in 8-liter units, wherein three part agents are contained in respective bottles. The stabilizer replenisher is available in 10-liter units, wherein two part agents are contained in respective bottles. These replenishing agents are stored and transported in respective outer packages of various sizes. The outer package size ranges from about 17.times.14.times.16.5 cm for the stabilizer replenisher to about 18.5.times.30.5.times.22.5 cm for the bleach-fixer replenisher; it is not possible to pile packages of replenishers in storing or transporting them or in storage them at dealer shops unless they are of the same kind, so that much space is required.
The third drawback concerns with the problem of waste container disposal. In recent years, there has been strong demand for environmental conservation and saving resources mainly in Europe and the United States; in the photographic industry, plastic container disposal has been of major concern. Specifically, although plastic containers for photographic use are cheap, conveniently storable and transportable and excellent in chemical resistance, they pose problems of accumulation in the environment because they are hardly biodegradable, and emission of large amounts of carbon dioxide upon burning, which contribute to global warming and acid rain. As for the problems posed on the user side, they include decrease in the available working area due to occupation of the narrow working space by crowding plastic containers, which are too tough to compress.
The fourth drawback is poor chemical stability.
Usually, the life time of a replenisher is at most 2 weeks even in the presence of a floating lid. However, with the trend toward replenishing rate reduction, it has recently been often the case where a 10-liter replenisher is used over a period of more than 1 month in a mini-lab receiving an order of 30 rolls of color films daily on average.
In this case, the replenisher in the replenishing tank is often much more frequently in contact with air than the processing solution in the processing tank; often, replenishing has no effect due to replenisher deterioration. Accordingly, attempts have been made to reduce the replenishing tank capacity to 5 liter or reduce the replenishing kit unit to 5 liter. However, this approach involves another drawback of the necessity of additional packing material.
For example, in preparing a color developer replenisher for color printing paper, a given volume of water is placed in the replenisher tank, after which dense kit A, which contains a preservative, is added, followed by stirring, and dense kit B, which contains a color developing agent, is then added, followed by stirring, and dense kit C, which contains an alkaline agent, is then added, followed by stirring, and finally water is added to make a given volume. This series of procedures is liable to be accompanied by some problems. For example, in case of insufficient stirring or a failure to add the starting water, the color developing agent tends to crystalize, and the resulting crystal can stay in the bellows pump and fail to be supplied so that the photographic performance becomes labile or the bellows pump breaks. Also, the dense kits are not always used immediately after production; they may be used even 1 year after production; in some cases, performance becomes labile due to oxidation of the color developing agent or preservative.
The color developer replenisher prepared from dense kits or powder is also known to pose some problems in the replenisher tank. For example, if the replenisher remains unused for a long time, crystals can deposit on the inside wall of the replenisher tank, the replenisher becomes susceptible to oxidation, and tar forms. Under some storage conditions, other problems arise, including separation of easily-crystallizing components of the replenisher, such as the color developing agent, at low temperatures; some makers specify replenisher storage conditions and instruct the users to keep their replenishers under those conditions.
As stated above, when a replenisher, e.g., a color developer replenisher for color printing paper, is prepared using a commonly used dense kit or powder, the above-mentioned problems arise; similar problems arise in the case of bleach-fixer, bleacher and fixer. For example, the bleach-fixer is characterized by considerably poor storage stability. This is because the bleach-fixer is usually of high acidity and considerably low pH for neutralizing the alkalinity of the dye fixer carried over by the printing paper being processed because the bleach-fixing process immediately follows the process with a color developer of high pH. It is said that at low pH values, any bleach-fixer comprising a thiosulfate and an oxidant is considerably poor in storage stability and cannot be replenished at low replenishing rates. The same applies to the fixer and stabilizer.
Another problem is that the replenisher becomes increasingly dense in answer to the recent trend toward replenishing rate reduction and rapid processing; it has recently been a common practice to concentrate the replenisher to the limit of solubility.
This deteriorates replenisher storage stability, thus posing many practical problems such as crystal separation.
On the other hand, in addition to the above method of preparing a replenisher using a dense kit or powder, another method is known wherein a dense kit is added as such.
In this method, supplying means such as a bellows pump are used to supply the dense kit as such directly to the processing tank and a given volume of replenishing water is added independently, to improve the low efficiency in dissolving operation. This method really obviates solution preparing operation and is free of the problem of poor storage stability because no replenisher solution is prepared, in comparison with the above method, wherein the replenisher is prepared from a dense kit or powder.
However, this method also involves many problems. The major problem is the increased size of the automatic processing machine because of the necessity for a dense kit tank for supplying the dense kit and a pump for supplying the dense kit. For example, in the case of CPK-2-20, a processing solution for color printing paper, the dense kit of color developer replenisher is divided in three parts; the dense kit of bleach-fixer replenisher, three parts; and the dense kit of stabilizer replenisher, two parts. To supply all these dense kits, eight tanks and eight pumps are required. In the conventional replenishing method, three tanks and three pumps are sufficient, since each replenisher requires one tank and one pump. In short, more tanks and more pumps than in the conventional method are required for supplying the dense kits, and a pump for water used to prepare the replenisher is also required. Also, since bellows pump precision is not so high, it is difficult to accurately discharge a plurality of solutions simultaneously, which can result in an imbalanced composition.
Moreover, dense kits are difficult to maintain due to proneness to crystallization near the outlet of replenisher nozzle because they are dense solutions. Another problem is that the bellows pump is insufficient in supplying accuracy so that replenishing accuracy fluctuates widely in supplying a dense replenisher, resulting in very labile photographic performance. Still another problem is that the amount of waste plastic containers remains unchanged, in comparison with the conventional replenishing method, even when dense kits are supplied.
In addition to the above methods, some proposals have been made to obviate the use of plastic containers and improve replenisher chemical stability.
For example, Japanese Patent Publication Open to Public Inspection (hereinafter referred to as Japanese Patent O.P.I. Publication) No. 11032/1983 discloses an art wherein developing components are encapsuled in microcapsules; Japanese Patent O.P.I. Publication No. 61837/1976 discloses photographic tablets containing a disintegrating agent. Japanese Patent O.P.I. Publication Nos. 109042/1990, 09043/1990, 39735/1991 and 39739/1991 disclose methods using granular photographic processing agents having a particular average grain size.
The photographic tablets containing a disintegrating agent described in Japanese Patent O.P.I. Publication No. 61837/1976 are merely easily-soluble tablets. This proposal never leads to the idea of the present invention that a solid processing agent is added directly to the processing tank and dissolved therein.
Japanese Patent O.P.I. Publication No. 109042/1990 describes a granular photographic processing agent having a particular average grain size.
However, none of these publications proposes an automatic processing machine which has sufficiently simplified operability free of replenisher dissolving operation and which offers stable photographic performance or a compact automatic processing machine having no replenisher tanks.
On the other hand, as a means for obviating the necessity for previous dissolving operation, Japanese Patent O.P.I. Publication No. 11344/1991 discloses an art wherein pasty part agents, in amounts according to the mixing ratio of the part agents, are pushed out from respective unit containers and appropriately diluted at given dilution rates to accurately prepare and supply replenishers. Although this method really reduces or almost obviates the necessity for dissolving operation, pasty part agents are unstable because of the presence of solvent and are difficult to push out in given amounts for long periods, and in addition, when they are used at low frequencies, nozzle clogging tends to occur, which hampers the obtainment of constant photographic performance. Also, paste containers are required, which must be made of a flexible and tough material, usually a composite material, which is usually difficult to recycle and is hence undesirable from the viewpoint of environmental protection. Particularly, pasty chemicals are known to be poor in storage stability due to the use of organic solvent to prepare the paste.
Japanese Utility Model Publication No. 85732/1989 discloses an automatic processing machine having a means for adding a tablet fungicide to the stabilizer, but this never leads to the idea of a processing agent replenishment controlling means, since the fungicide itself poses no problem even in the event of entry in large amounts, and in addition, the addition of such a fungicide is essential, since its purpose is to preserve the stabilizer.
WO 91-07698 and WO 91-07699 disclose a method wherein CD-3 or CD-4 is added in a solid form while the other components added as activators in the form of liquid. However, the relevant patents concern with regeneration, particularly low rate replenishment involving almost no overflow, specifically a method wherein bromide and chloride ions are adsorbed and removed from the developer by means of ion exchange resin, after which the lacking components, namely alkali agent activator and a small amount of solid or liquid dense color developing agent are added while maintaining a constant volume.
The present invention is totally different from the inventions described above in that processing agent replenishment is achieved solely by adding a removely weighed solid processing agent to the processing tank and dissolve it therein, whereby previous replenisher dissolving operation is obviated to ensure maintenance-free operation; the present invention is never expected from the above invention.
On the other hand, it was proven that a solid processing agent has the following problems. Since a solid processing agent is composed of materials dissolvable in a processing solution entirely, it is effected by water to be deformed, in most cases due to humidity.
When such an altered solid processing agent is supplied to a processing solution, it was proven that not only deterioration in processing ability of aforesaid processing solution is caused but also various adverse influences take place in automatic processing machine itself, especially to a solid processing agent supplying means or a housing means causing problems. In other words, it was proven that, due to partial dissolution of the solid processing agent cause by moisture, elements of solid processing agent dissolved stick inside the solid processing agent supplying device in the automatic processing machine or inside the housing means causing contamination. Or, when a solid processing agent is a tablet or a pill, solid processing agents adjoining each other are forced to be sticked together due to moisture. On the other hand, when a solid processing agent is a powder or a granule, solid processing agents are joined to form a large clumps due to humidity, resulting in caking. In any case, when solid processing agents are clogged at the supplying port of the solid processing agent supplying device to a processing tank, the prescribed amount of supplying may be stopped, causing problem. In addition, with regard to processing solution quality too, increase of the moisture content ratio in the solid processing agent due to high humidity promotes oxidation and sulfurization of the components in the solid processing agents, which causes lowering of property resulting in problems.
Technologies for solving the above-mentioned problems have already been described in Japanese Patent Application Nos. 107713/1993, 107714/1993, 107715/1993 and 107716/1993 by the present inventor.
However, the above-mentioned applications relates to apparatuses preventing soaking of solid processing agents inside the supplying device due to splashing of the processing solution when aforesaid solid processing agent is supplied to the processing solution in the automatic processing machine directly. Accordingly, wetting of solid processing agents and deformation thereby due to the entering of vapor which generates from the automatic processing machine to aforesaid supplying device, no consideration was paid, or only insufficient consideration was paid.
On the other hand, Japanese Patent OPI Publication No. 213454/1992 discloses a device provided with an exhausting port and a conveyance section in a dehumidified space closed tightly in an automatic processing machine wherein a granular processing agent is added to a processing tank. In this apparatus, aforesaid solid processing agent can be protected from humidity by means of a methods to use package provided with a dehumidifying treatment until it is housed to a solid processing agent supplying device. However, once the agent is housed to the supplying device, it may be kept as it is for 1 month or more in an automatic processing machine with low replenishing processing. In this meaning, in the case that the humidity outside is high such as in the summer season in Japan, or in the case aforesaid processing machine is installed in a place where humidity is regarded as high normally, the above-mentioned patent application did not pay any consideration on a measure against wetting and deformation when aforesaid solid processing agent is exposed to air outdoor with high humidity.
Especially, since a light-sensitive material is processed in an automatic processing machine in such a manner that the a processing solution is kept at a certain temperature, evaporation of the processing solution occurs and also evaporation of moisture from the light-sensitive material in a drier section in the automatic processing machine occurs. Accordingly, the humidity surrounding the automatic processing machine is liable to be high by nature, causing the above-mentioned problem noticeably.
The following issues are further cited as conventional problems:
In an automatic processing machine wherein a conventional processing agent is dissolved for a replenisher solution in advance and processing operation is conducted while supplying the replenisher solution into a processing tank when necessary, water is required for dissolution and dilution of the processing agent iwhen a replenishng water is supplied and for supplementation of evaporation from the processing solution.
In order to feed water from a water supplying source such as tap water to an automatic processing machine, there may be a method to connect the tap water and the automatic processing machine directly. However, since many problems exist such as that the conditions for establishing the automatic processing machine and a water piping are controlled strictly, the above-mentioned method is not used commonly. Accordingly, in most cases, a method to convey water manually from the water supplying source located near the automatic processing machine is adopted. However, this work requires much labor to persons who use the automatic processing machine. Especially, when there is no water supplying source near the automatic processing machine, it is necessary to convey water from a distance, and in some cases, water must be conveyed from the lower floor, resulting in very insufficient automatic operation.
In addition, recently there has been a trend in automatic processing machines for down-sizing. following it, automatic processing machines began to be installed in places where automatic processing machines had not been installed previously. In general, most of such places do not have a ready water supply source closely, resulting in troublesome water supplying work requesting labor as stated above. This is another problem.
In an automatic processing machine wherein the solid processing agent of the present invention is dissolved directly in a processing tank, it is desirable to sense the amount of processing of a photographic light-sensitive material at the same time as supplying the solid processing agent before supply replenishing water and to keep photographic properties at a constant level by diluting reaction inhibiting components eluted arising from processing. The water supplying work for this has still remained necessary. This is still another problem.
On the other hand, a method to dehumidify air taken into an automatic processing machine and to supply water generated there to a processing tank or a tank for a replenisher solution is disclosed in Japanese Patent OPI. Publication No. 219245/1991. In addition, a method to supply water obtained by concentrating vapor exhausted from the drier section and a processor section to the processor section is disclosed in Japanese Patent OPI. Publication No. 78851/1992. The purpose of these two applications is to obtain water for a method and an apparatus for processing light-sensitive materials while supplying a replenisher solution from the tank for a replenisher solution to the processing tank when necessary and water for compensating for evaporation of the processing solution. Accordingly, these applications cannot foresee the concept of the present invention to keep replenishing water in an automatic processing machine of the present invention wherein solid processing agents are dissolved into the processing tank directly and to result in maintenance-free function because replenishing solution is not necessary to be prepared.
In addition, in methods and apparatuses wherein an device like a dehumidifier is provided in an automatic processing machine which processes light-sensitive materials while supplying a replenishing solution from a conventional tank for replenishing solution in the relevant field to a processing tank when necessary, in addition to a supplying means for replenisher for processing solution, a means for controlling supplying and tanks, both of which are necessary for replenishing water use removely. Accordingly, when comparing with a method wherein similar devices are provided in an automatic processing machine of the present invention which dissolves solid processing agents directly to the processing tank, the automatic processing machine becomes complicated and unwieldy. This is another problem.
In addition, in Japanese Patent OPI. Publication No. 219245/1991, a method to obtain water by dehumidifying air taken in by a drier is disclosed. However, it also is a method and an apparatus for processing light-sensitive materials while supplying a replenishing solution into a processing tank when necessary. The object of this method and apparatus is to obtain water for dissolving or diluting processing agent when a replenishing solution is produced and water supplementing vapor from the processing solution. Accordingly, they cannot foresee the concept of the present invention to make maintenance-free function because it is not necessary to keep replenishing water and to prepare a replenishing solution in an automatic processing machine of the present invention wherein solid processing agents Are dissolved directly to a processing tank and to prevent deformation of solid processing agents due to humidity.
On the other hand, in Japanese Patent OPI. Publication No. 78851/1992, a separate device to return water obtained by a vapor condenser placed above the processing tank to the above-mentioned processing tank placed below thereof. The object of this invention is to obtain water for supplementing vapor from a processing solution in a method and an apparatus to process light-sensitive materials while supplying replenishing solution from a tank for a replenishing solution to a processing tank when necessary. Accordingly, from this, the concept of the present invention to keep replenishing water in an automatic processing machine of the present invention wherein solid processing agents are dissolved into a processing tank directly is not foreseeable.
In addition, in the invention disclosed in Japanese Patent OPI. Publication No. 78851/1992, a condenser must be provided to each processing tank. Accordingly, not only that the automatic processing machine becomes complicated and large in size in total but also that troublesome water supplying work remains necessary for supplementing moisture for other purposes such as diluting water necessary for processing light-sensitive materials though evaporation can be supplemented to some extent.
On the other hand, apart from the above-mentioned method, a technology to reuse effluent for reducing the amount of effluent was disclosed in Japanese Patent OPI Publication No. 174154/1991. This is extremely effective for reducing the amount of effluent. In addition, it has a benefit that concentration of replenisher is not necessary to some extent. However, a stock tank is required for each processing tank and a dissolution tank is additionally required. Only with them, enormous space is required. In addition, due to the existence of dissolution operation, troublesomeness for it is not lightened. Furthermore, when an overflowed solution is recycled completely, elusion from a light-sensitive material is accumulated. Accordingly, in order to dilute or reduce accumulated material, part of it is abolished or recycled by means of ion-exchanged resin. Accordingly, it causes some problems on a mini-lab or the like.
However, the above-mentioned photo-effluent causes extremely severe pollution and regulations against environmental pollution have recently been enforced. Accordingly, it is substantially impossible to drain photo-effluent into sewage systems or rivers. Therefore, currently, photo-effluent is collected and disposed by specialized firms. However, a method of entrusting disposing effluent to such firms for disposing effluent has shortcomings since considerable space for storing effluent and expensive cost for collection. In addition, extremely large-scale facilities are necessary for disposing of effluent in an environmentally friendly manner. For installing such a disposing facilities, enormous cost is required and cost for disposing also become expensive. Accordingly, some of effluent collected is dumped into the ocean. Since entire prohibition on dumping into the ocean is pressing now from the viewpoint of protecting worldwide environment, disposal of effluent has come to be a critical problem to our industry.
In addition, as stated above, that replenishing water is necessary means that the supply source for the replenishing water must be located in the vicinity from the processing plants. Recently, following prevailing of mini-labs and micro-labs, the number of cases in which photographic processing must be conducted where there is no tap water closely has been increased. Accordingly, keeping water has become a critical problem. This problem is especially critical when a solid processing agent is used. It is no exaggeration to say that it is an only maintenance activity conducted by manual. In order to solve these problems, a technology to reuse distilled liquid generated from evaporation of photo-effluent is disclosed in Japanese Patent OPI. Publication No. 201442/1987. However, the object of this method is to produce a replenisher by mixing a solution in the dissolution tank. Therefore, it is considerably different from the object of the present invention to pursue maintenance-free function so that it is impossible to foresee the present invention. In addition, in Japanese Patent OPI. Publication No. 78746/1991 discloses a method to introduce dry heat in a effluent tank for reusing the resulting moisture. However, no concept and technology for eliminating dissolution operation of the present invention and provide maintenance-free function were disclosed. Accordingly, it is completely different from the present invention. In addition, Japanese Patent OPI. Publication No. 219245/1991 discloses a method to supply moisture generated by the use of Peltier element to the processing tank in the same manner as the preceding invention. However, neither its structure nor technological concept were the same as the present invention.
In addition, it is common that replenishing water is stored in a plastic bucket in the form of water. It is gradually fed to the processing tank. Accordingly, the time of storage in the stock tank is frequently elongated so that propagation of mildew and bacteria is easily to occur. When mildew and bacteria are also fed with replenishing water, a large amount of gelatin contained in a color paper or the like becomes a suitable victim to them, easily causing deterioration of images after being stored. In addition, not only mildew or bacteria, heavy metal components and sulfur components due to rust may be contained in water used as a supplying source for replenishing water, neither of which is acceptable in terms of photographic processing stability. Only in replenishing water, all of the above-mentioned problems are potential so that immediate solution is urged.